CN107941883A - A kind of preparation method of gastrodin molecular engram electrochemical sensor - Google Patents

Abstract

The invention discloses a kind of preparation method of gastrodin molecular engram electrochemical sensor; using Gastrodin as template molecule, Oridonin be function monomer, azodiisobutyronitrile is initiator, nanoclay is dopant; crosslinking agent is used as to coumaric acyl tyrasamine so that N is trans; the gastrodin molecular engram electrochemical sensor of highly sensitive nanoclay doping is prepared for accordingly; the analysis method is simple and practical, overcomes the shortcomings that conventional analysis method is complicated, equipment is expensive, sensitivity is low.

Description

A kind of preparation method of gastrodin molecular engram electrochemical sensor

Technical field

The present invention relates to molecular imprinting electrochemical sensor, especially a kind of gastrodin molecular engram electrochemical sensor Preparation method.

Background technology

Gastrodin (Gastrodin) is also known as gastrodin, and it is excited between process of inhibition that Gastrodin can recover cerebral cortex Dysequilibrium, has preferable decompression, calm, syngignoscism, has certain curative effect, moreover it is possible to expand to neurasthenia, insomnia headache Blood vessel, improve Myocardial Microcirculation, alleviate cerebral angiospasm, increase cardiac muscle nutritional blood flow raising oxygen delivery capacity, is middle treatment Treat dizziness of having a headache, extremity numbness, the main ingredient of frightened pain twitch.Appropriate take this medicine can improve sleep, be good for your health, but long Phase or such medicine, which is excessively used, to cause appetite to subtract greatly, weight loss, in addition it is dead.

The method of measure Gastrodin has Gradient Elution method, reversed-phase high performance liquid chromatography-diode array Method and capillary electrophoresis etc..But these methods are due to needing expensive instrument and equipment, there are it is of high cost, time-consuming, sensitive The shortcomings of degree is not high.Therefore, study a kind of high sensibility, easy Gastrodin assay method has very important significance.

Molecular imprinting technology is using target molecule to be measured as template molecule, will be led to functional monomer complementary in structure Cross covalently or non-covalently key and template molecule and combine to form monomer template molecular complex, add crosslinking agent be allowed to monomer into Row polymerisation forms template molecule polymer, by either physically or chemically removing template molecule after the completion of reaction, is divided Sub- imprinted polymer, forms complementary and with Multiple recognition site the sky with former microsphere space structure in the polymer Cave.Current method is since the function monomer of selection cannot be properly matched with template molecule, and crosslinked rigidity is also poor, Therefore sensitivity is not high.

The content of the invention

The technical problem to be solved in the present invention is to provide a kind of equipment it is simple, make a kind of easy gastrodin molecular engram The preparation method of electrochemical sensor.

In order to solve the above technical problems, the present invention adopts the following technical scheme that：Using Gastrodin as template molecule, Rabdosia rubescens first Element is function monomer, azodiisobutyronitrile is initiator, nanoclay is dopant, using N- it is trans-to coumaric acyl tyrasamine as It is prepared by crosslinking agent.

A kind of preparation method of above-mentioned gastrodin molecular engram electrochemical sensor, is insulted by template molecule, winter of Gastrodin Careless A prime is function monomer, azodiisobutyronitrile be initiator, using N- it is trans-coumaric acyl tyrasamine is glued as crosslinking agent, nanometer Soil is dopant, and it is thin to form a kind of hybridized nanometer clay gastrodin molecular engram polymers in 2 mm glassy carbon electrode surfaces of diameter Film, then using eluant, eluent molar ratio 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.

A kind of preparation method of above-mentioned gastrodin molecular engram electrochemical sensor, comprises the following steps：

<1>Into 10.0 mL etoh solvents, the mmol template molecules Gastrodin of 0.1 mmol~1.5,1.0 mmol are sequentially added ~6.0 mmol function monomers Oridonins, 1.5 mmol crosslinking agents N- are trans-to coumaric acyl tyrasamine, 0.15 The nanoclay of the g of mmol initiator azodiisobutyronitriles and 0.0100 g~0.0600, often adds a kind of chemical reagent ultrasonic wave Dissolving 8 minutes；

<2>Take step<1>6 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.

Research finds, be function monomer using Gastrodin as template molecule, Oridonin, azodiisobutyronitrile be initiation Agent, nanoclay are dopant, using N- it is trans-the gastrodin molecular engram electrochemistry that is prepared to coumaric acyl tyrasamine as crosslinking agent Sensor, the content available for measure Gastrodin.The electrochemical analysis method for measuring Gastrodin is established using the present invention, is had very Outstanding sensitivity；The concentration of Gastrodin is 2.5 × 10^-8 ~ 4.0×10^-4Good linear relationship is presented in the range of mol/L (linearly dependent coefficient is R=0.9998), detection limit (S/N=3) it is 3.5 × 10^-9Mol/L, therefore, nanoclay doping Gastrodin molecular engram electrochemical sensor there is higher sensitivity, more than current detection method；And equipment is simple, Make simple.

Brief description of the drawings

Fig. 1 is a kind of working curve diagram of the preparation method of gastrodin molecular engram electrochemical sensor in embodiment 1.

Embodiment

Embodiment 1

First, the processing of glass-carbon electrode

Glass-carbon electrode is polished with 1.0 μm, 0.3 μm and 0.05 μm of alumina powder successively on polishing cloth, is then placed in body Product is than being 1:8 min of ultrasound in 1 nitric acid, place into 8 min of ultrasound in absolute ethyl alcohol, are finally cleaned by ultrasonic with pure water clean.

2nd, the preparation of gastrodin molecular engram electrochemical sensor

<1>Into 10.0 mL etoh solvents, 0.6 mmol template molecules Gastrodin, 1.5 mmol function monomer winters are sequentially added Insult careless A prime, 1.5 mmol crosslinking agents N- it is trans-to coumaric acyl tyrasamine, 0.15 mmol initiator azodiisobutyronitriles and The nanoclay of 0.0400 g, often adds a kind of chemical reagent ultrasonic wave and dissolves 8 minutes；

<2>Take step<1>6 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio 1:1 acetic acid and propanol solvent mixture are by template molecule elution, by magnetic agitation eluted template molecule, until being detected in eluent Less than template molecule, then the solvent of trace electrode surface is washed away with ultra-pure water, then trace electrode is stored in ultra-pure water and is treated With.

3rd, the measure of the drafting of working curve and detection limit

The experiment of the gastrodin molecular engram electrode response characteristic of nanoclay doping is carried out with differential pulse voltammetry, measures line Property scope and detection limit.By the gastrodin molecular engram electrode of nanoclay doping respectively in the Gastrodin solution of various concentrations Cultivate 6 minutes（Bottom liquid is 5.0 mmol/L K₃[Fe(CN)₆] -0.5 mol/L pH=7.5 phosphate buffer solution it is molten Liquid）, then carry out differential pulse voltammetry measurement.Gastrodin solution concentration is 2.5 × 10^-8 ~ 4.0×10^-4Mol/L scopes It is interior that good linear relationship is presented；Linear equation isIP (μ A)=8.683 с (μm ol/L)+1.048, linearly dependent coefficient are R=0.9998, detection limit (S/N=3) it is 3.5 × 10^-9 mol/L。

Therefore, the gastrodin molecular engram electrode of nanoclay doping has high sensitivity.

Claims (1)

1. a kind of preparation method of gastrodin molecular engram electrochemical sensor, it is characterised in that with 0.01 mmol/mL~0.15 The Gastrodin of mmol/mL is template molecule, the Oridonin of the mmol/mL of 0.10 mmol/mL~0.60 be function monomer, The azodiisobutyronitrile of 0.015 mmol/mL be initiator, using the N- of 0.15 mmol/mL it is trans-to coumaric acyl tyrasamine as friendship Join agent, the nanoclay of the g/mL of 0.0010 g/mL~0.0060 is dopant, a kind of hydridization is formed in glassy carbon electrode surface Nanoclay gastrodin molecular engram polymers film, then using eluant, eluent acetic acid and propanol solvent mixture eluted template molecule To obtain the final product；

Specifically carried out by following operation：

<1>Into 10.0 mL etoh solvents, the mmol template molecules Gastrodin of 0.1 mmol~1.5,1.0 mmol are sequentially added ~6.0 mmol function monomers Oridonins, 1.5 mmol crosslinking agents N- are trans-to coumaric acyl tyrasamine, 0.15 The nanoclay of the g of mmol initiator azodiisobutyronitriles and 0.0100 g~0.0600, often adds a kind of chemical reagent ultrasonic wave Dissolving 8 minutes；

<2>Take step<1>6 μ L of mixture be applied in the glassy carbon electrode surface of clean smooth a diameter of 2 mm, it is small to place 6 Shi Hou, when the electrode after modification is placed in thermal polymerization 1.5 is small in 85 DEG C of vacuum drying chamber, then using eluant, eluent molar ratio For 1:1 acetic acid and propanol solvent mixture are by template molecule elution, to obtain the final product.